+

WO2019176965A1 - Composite pour former une électrode, procédé de fabrication d'électrode, et procédé de fabrication d'élément de stockage électrique non aqueux - Google Patents

Composite pour former une électrode, procédé de fabrication d'électrode, et procédé de fabrication d'élément de stockage électrique non aqueux Download PDF

Info

Publication number
WO2019176965A1
WO2019176965A1 PCT/JP2019/010100 JP2019010100W WO2019176965A1 WO 2019176965 A1 WO2019176965 A1 WO 2019176965A1 JP 2019010100 W JP2019010100 W JP 2019010100W WO 2019176965 A1 WO2019176965 A1 WO 2019176965A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite
forming
positive electrode
electrode
active material
Prior art date
Application number
PCT/JP2019/010100
Other languages
English (en)
Inventor
Eiko Hibino
Toru Ushirogochi
Toshiya Sagisaka
Satoshi Nakajima
Hiromichi KURIYAMA
Masahiro Masuzawa
Keigo TAKAUJI
Miku OHKIMOTO
Hiromitsu Kawase
Original Assignee
Ricoh Company, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2019003695A external-priority patent/JP2019164993A/ja
Application filed by Ricoh Company, Ltd. filed Critical Ricoh Company, Ltd.
Priority to US16/975,968 priority Critical patent/US20210005876A1/en
Priority to EP19715242.4A priority patent/EP3766111A1/fr
Priority to CN201980017838.2A priority patent/CN111819709A/zh
Priority to KR1020207025784A priority patent/KR20200117014A/ko
Publication of WO2019176965A1 publication Critical patent/WO2019176965A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a composite for forming an electrode, a method of manufacturing an electrode, and a method of manufacturing a nonaqueous electric storage element.
  • Lithium-ion secondary batteries have been installed in mobile devices, hybrid vehicles, electric vehicles, and the like, and the demand has been expanding. Also, there is a growing need for thin batteries to be installed on various wearable devices and medical patches, and requirements for lithium-ion secondary batteries have been diversifying.
  • the coating material generally has a binder dissolved in an organic solvent or in water and has a viscosity of several thousands to several tens of thousands mPa ⁇ s at 25 °C.
  • the inkjet method is a method of discharging special ink as fine droplets from nozzles on a head, which includes a piezo method, a thermal method, and a valve method depending on the structure of the head for discharging the ink.
  • the piezo method has advantages such that the amount of ink to be discharged can be precisely controlled by controlling the voltage; influence on the use environment is small because heat is not applied; and the durability is high.
  • a composite for forming an electrode that can be discharged by the inkjet method generally has a viscosity of single-digit to several hundreds mPa ⁇ s at 25 °C, which is smaller than a viscosity of a conventional coating material at 25 °C. Also, in order to stably and continuously execute discharging without clogging nozzles on a head, especially when using the piezo method, it is necessary to adjust the viscosity and the surface tension of the composite for forming an electrode to appropriate values.
  • alkali-metal-containing transition metal compound for example, a lithium-containing transition metal compound such as a complex oxide containing lithium and one or more elements selected from among a group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium, may be considered.
  • a lithium-containing transition metal compound such as a complex oxide containing lithium and one or more elements selected from among a group consisting of cobalt, manganese, nickel, chromium, iron, and vanadium, may be considered.
  • lithium-containing transition metal compound for example, a lithium-containing transition metal oxide such as lithium cobalt oxide, lithium nickel oxide, lithium manganate, and the like may be listed.
  • the polyanion-based compound it is favorable for the polyanion-based compound to have its surface covered and compound with a conductive aid such as a carbon material.
  • carbon material for example, natural graphite, artificial graphite, non-graphitizable carbon (hard carbon), easily graphitizable carbon (soft carbon), and the like may be listed.
  • lithium titanate titanium oxide, and the like may be listed.
  • the composite for forming an electrode according to the present embodiment is nonaqueous.
  • the content of water in the composite for forming an electrode according to the present embodiment is favorably less than or equal to 5 mass%, and more favorably less than or equal to 1 mass%. This enables to prevent lithium contained in the active material from reacting with water to form a compound such as lithium carbonate and to reduce the discharge capacity of the nonaqueous storage element. This also enables, while charging or discharging the nonaqueous electric storage element, to prevent generation of gas due to decomposition of a compound such as lithium carbonate.
  • the D 10 of the active material is favorably greater than or equal to 0.1 ⁇ m, and more favorably greater than or equal to 0.15 ⁇ m.
  • the storage stability of the composite for forming an electrode according to the present embodiment is further improved.
  • conductive carbon black formed by a furnace method, an acetylene method, a gasification method, or the like may be used; other than these, a carbonaceous material such as carbon nanofibers, carbon nanotubes, graphene, graphite particles, or the like may be used.
  • polyphenylene sulfide particles as the macromolecular particles
  • the dispersing agent for example, polyoxyethylene cumyl phenyl ether as a surfactant having a phenyl group may be used.
  • the method of manufacturing an electrode according to the present embodiment includes a process of discharging a composite for forming an electrode according to the present embodiment onto an electrode substrate. At this time, by drying the composite for forming an electrode discharged onto the electrode substrate, an electrode mixture can be formed.
  • the method of manufacturing an electrode according to the present embodiment may further include a process of pressing the electrode substrate onto which the composite for forming an electrode has been discharged.
  • FIG. 1 illustrates an example of an electrode manufactured by the method of manufacturing an electrode according to the present embodiment.
  • the material constituting the positive electrode substrate for example, stainless steel, aluminum, titanium, tantalum, and the like may be listed.
  • the material constituting the negative electrode substrate for example, stainless steel, nickel, aluminum, copper, and the like may be listed.
  • the method of manufacturing a nonaqueous electric storage element according to the present embodiment includes a process of manufacturing an electrode by using the method of manufacturing an electrode according to the present embodiment.
  • the nonaqueous electric storage element may further have constituent members such as an outer can, electrode lead wires, and the like, when necessary.
  • FIG. 2 illustrates an example of a nonaqueous electric storage element manufactured by the method of manufacturing a nonaqueous electric storage element according to the present embodiment.
  • a nonaqueous electric storage element 20 has a positive electrode 21, a negative electrode 22, a separator 23 holding a nonaqueous electrolytic solution, an outer can 24, a lead wire 25 of the positive electrode 21, and a lead wire 26 of the negative electrode 22.
  • the nonaqueous electrolytic solution is an electrolytic solution in which an electrolyte salt (in particular, an electrolyte salt containing halogen atoms) is dissolved in a nonaqueous solvent.
  • an electrolyte salt in particular, an electrolyte salt containing halogen atoms
  • chain carbonate for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), methylethyl carbonate (EMC), and the like may be listed.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC methylethyl carbonate
  • an ester-based organic solvent such as cyclic ester, chain ester, or the like
  • an ether-based organic solvent such as cyclic ether, chain ether, or the like
  • ⁇ -butyrolactone ⁇ BL
  • 2-methyl- ⁇ -butyrolactone 2-methyl- ⁇ -butyrolactone
  • acetyl- ⁇ -butyrolactone ⁇ -valerolactone, and the like may be listed.
  • cyclic ether for example, tetrahydrofuran, alkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxolane, and the like may be listed.
  • chain ether for example, 1,2-dimethoxyethane (DME), diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, and the like may be listed.
  • DME 1,2-dimethoxyethane
  • diethyl ether ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, and the like
  • DME 1,2-dimethoxyethane
  • diethyl ether diethyl ether
  • ethylene glycol dialkyl ether diethylene glycol dialkyl ether
  • triethylene glycol dialkyl ether triethylene glycol dialkyl ether
  • tetraethylene glycol dialkyl ether tetraethylene glycol dialkyl ether
  • the electrolyte salt is not limited in particular as long as having a high ionic conductivity and being soluble in a nonaqueous solvent.
  • the electrolyte salt contains halogen atoms.
  • lithium ions for example, lithium ions or the like may be considered.
  • As anions constituting the electrolyte salt for example, BF 4 - , PF 6 - , AsF 6 - , CF 3 SO 3 - , (CF 3 SO 2 ) 2 N - , (C 2 F 5 SO 2 ) 2 N - , and the like may be listed.
  • the lithium salt is not limited in particular and may be appropriately selected in accordance with the purpose; for example, lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium arsenic hexafluoride (LiAsF 6 ), lithium trifluoromethasulfonate (LiCF 3 SO 3 ), lithium bis (trifluoromethylsulfonyl) imide (LiN(CF 3 SO 2 ) 2 ), lithium (bispentafluoroethylsulfonyl) imide (LiN(C 2 F 5 SO 2 ) 2 ), and the like may be listed.
  • LiPF 6 is favorable from the viewpoint of ion conductivity
  • LiBF 4 is favorable from the viewpoint of stability.
  • one material may be used alone, or two or more may be used together as the electrolyte salt.
  • separator for example, paper such as kraft paper, vinylon mixed paper, and synthetic pulp mixed paper; polyolefin non-woven fabric such as cellophane, polyethylene graft film, polypropylene melt-blown non-woven fabric; polyamide non-woven fabric; glass fiber non-woven fabric; micropore film; and the like, may be listed.
  • the structure of the separator may be a monolayer structure or a laminate structure.
  • nonaqueous electric storage element Uses of the nonaqueous electric storage element are not limited in particular and it can be used for various uses; for example, laptop computers, pen-input personal computers, mobile personal computers, electronic book players, mobile phones, portable fax machines, portable copiers, portable printers, headphone stereos, video movie players, liquid crystal televisions, handy cleaners, portable CD players, mini discs, transceivers, electronic diaries, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, lighting devices, toys, game machines, strobes, cameras, and the like may be listed.
  • the particle-size distribution of an active material dispersed in water was measured by using a laser-diffraction particle-size distribution measuring device.
  • An E-type viscometer (cone/plate viscometer) having a rotor of No. CPA-40Z attached was used to measure the viscosity of a composite for forming an electrode with 100 rpm at 25 °C.
  • the particle-size distribution of macromolecular particles dispersed in a main dispersion medium and a composite for forming an electrode was measured by using a laser-diffraction particle-size distribution measuring device.
  • Lithium cobalt oxide (LiCoO 2 ) particles (manufactured by Sigma-Aldrich Co.) were crushed by a jet mill so that the D 90 became less than 3 ⁇ m, to obtain a positive electrode active material (3) having a peak in the particle-size distribution at 0.9 ⁇ m.
  • Ni-Mn-Co (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) based particles were crushed by a jet mill so that the D 90 became less than 3 ⁇ m, to obtain a positive electrode active material (5) having a peak in the particle-size distribution at 0.9 ⁇ m.
  • Lithium manganate (LiMn 2 O 4 ) particles (manufactured by Sigma-Aldrich Co.) were crushed by a jet mill so that the D 90 became less than 3 ⁇ m, to obtain a positive electrode active material (6) having a peak in the particle-size distribution at 1.2 ⁇ m.
  • Lithium titanate (Li 4 Ti 5 O 12 ) particles (manufactured by Sigma-Aldrich Co.) were crushed by a jet mill so that the D 90 became less than 3 ⁇ m, to obtain a negative electrode active material (2) having a peak in the particle-size distribution at 0.7 ⁇ m.
  • Table 1 lists the species of active materials.
  • a composite for forming a positive electrode was prepared by mixing 25 mass% of the positive electrode active material (1); 5 mass% of Toraypearl TM PVDF (manufactured by Toray Industries, Inc.) as an aqueous dispersion of 20 mass% of polyvinylidene fluoride (PVDF) particles having an average particle diameter of 0.5 ⁇ m and a melting point at 151 °C; and 70 mass% of a mixed solution of ion-exchanged water and propylene glycol (mass ratio of 7:3).
  • Toraypearl TM PVDF manufactured by Toray Industries, Inc.
  • PVDF polyvinylidene fluoride
  • the particle-size distribution of the composite for forming a positive electrode was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 was 2.9 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a positive electrode was satisfactory.
  • the aluminum foil having the coating film formed was placed in a dryer at 120 °C for five minutes to dry and remove the solvent, and then, pressed by a roll press machine having the roll temperature set at 90 °C to form a positive electrode mixture so as to prepare a positive electrode.
  • the positive electrode was immersed in propylene carbonate as a nonaqueous solvent used in a nonaqueous electric storage element, to evaluate the adhesion of the positive electrode mixture; no floating or peeling of the positive electrode mixture was observed, and the positive electrode mixture stuck firmly on the aluminum foil. Thus, it was confirmed that the polyvinylidene fluoride particles function as a binder.
  • a composite for forming a positive electrode was prepared by mixing 25 mass% of the positive electrode active material (1); 2 mass% of an aqueous dispersion of 50 mass% of acrylic resin particles having an average particle diameter of 0.15 ⁇ m and a glass transition temperature at -61 °C; and 73 mass% of a mixed solution of ion-exchanged water and propylene glycol (mass ratio of 7:3).
  • acrylic resin exists as particles in the composite for forming a positive electrode, and the mixed solution of water and propylene glycol functions as a dispersion medium.
  • the viscosity of the composite for forming a positive electrode was 16 mPa ⁇ s.
  • the particle-size distribution of the composite for forming a positive electrode was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 was 3.1 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a positive electrode was satisfactory.
  • the aluminum foil having the coating film formed was placed in a dryer at 120 °C for five minutes to dry and remove the solvent, and then, pressed by a roll press machine at room temperature to form a positive electrode mixture so as to prepare a positive electrode.
  • the positive electrode was immersed in propylene carbonate as a nonaqueous solvent used in a nonaqueous electric storage element, to evaluate the adhesion of the positive electrode mixture; no floating or peeling of the positive electrode mixture was observed, and the positive electrode mixture stuck firmly on the aluminum foil. Thus, it was confirmed that the particles of acrylic resin function as a binder.
  • a composite for forming a negative electrode was prepared by mixing 15 mass% of the negative electrode active material (1); 1 mass% of BM-400B (manufactured by Nippon Zeon Co., Ltd.) as an aqueous dispersion of 50 mass% of styrene-butadiene copolymer particles having an average particle diameter of 0.15 ⁇ m and a glass transition temperature at -5 °C; 0.01 mass% of TRITON X-100 (manufactured by Sigma-Aldrich Co.) as a dispersing agent; and 83.9 mass% of a mixed solution of ion-exchanged water and propylene glycol (mass ratio of 7:3).
  • BM-400B manufactured by Nippon Zeon Co., Ltd.
  • TRITON X-100 manufactured by Sigma-Aldrich Co.
  • styrene-butadiene copolymer exists as particles in the composite for forming a negative electrode, and the mixed solution of water and propylene glycol functions as a dispersion medium.
  • the viscosity of the composite for forming a negative electrode was 14 mPa ⁇ s.
  • the particle-size distribution of the composite for forming a positive electrode was measured, and it was found that the distribution had a peak at 1.8 ⁇ m and the D 90 was 3.2 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a negative electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a negative electrode was satisfactory.
  • the negative electrode was immersed in propylene carbonate as a nonaqueous solvent used in a nonaqueous electric storage element, to evaluate the adhesion of the negative electrode mixture; no floating or peeling of the negative electrode mixture was observed, and the negative electrode mixture stuck firmly on the copper foil. Thus, it was confirmed that the styrene-butadiene copolymer particles function as a binder.
  • a composite for forming a positive electrode was prepared by mixing 25 mass% of the positive electrode active material (1) and 75 mass% of the aqueous solution of 1 mass% of sodium carboxymethylcellulose.
  • the viscosity of the composite for forming a positive electrode was 18 mPa ⁇ s.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, immediately after the start of printing, discharge defects were found in some nozzles, and as the printing continued, the number of discharge-defective nozzles continued to increase. For this reason, the discharge stability of the composite for forming a positive electrode was inadequate.
  • a composite for forming a positive electrode was prepared by mixing 5 mass% of the positive electrode active material (1); 15 mass% of the aqueous solution of 1 mass% of the carboxymethylcellulose sodium; and 80 mass% of a mixed solution of ion-exchanged water and propylene glycol (mass ratio of 7:3).
  • the viscosity of the composite for forming a positive electrode was 12 mPa ⁇ s.
  • the particle-size distribution of the composite for positive electrode formation was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 was 3.7 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a positive electrode was satisfactory.
  • a composite for forming a positive electrode was prepared by mixing 25 mass% of the positive electrode active material (1); 5 mass% of Toraypearl TM PPS (manufactured by Toray Industries, Inc.) as an aqueous dispersion of 10 mass% of polyphenylene sulfide (PPS) particles having an average particle diameter of 0.5 ⁇ m, a glass transition temperature at 85 °C, and a melting point at 285 °C; and 70 mass% of cyclohexanone.
  • Toraypearl TM PPS manufactured by Toray Industries, Inc.
  • PPS polyphenylene sulfide
  • polyphenylene sulfide exists as particles in the composite for forming a positive electrode, and the mixed solution of water and cyclohexanone functions as a dispersion medium. Also, the polyphenylene sulfide particles are dispersed in water because polyoxyethylene cumyl phenyl ether is used as a dispersing agent.
  • the viscosity of the composite for forming a positive electrode was 14 mPa ⁇ s.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, it was possible to continuously discharge the composite for forming a positive electrode, and the discharge stability of the composite for forming a positive electrode was satisfactory. Also, by printing the composite for forming a positive electrode eight times, it was possible to form a coating film corresponding to around 2.5 mg/cm 2 of the positive electrode mixture, and the printing efficiency of the composite for forming a positive electrode was satisfactory.
  • the positive electrode was immersed in propylene carbonate as a nonaqueous solvent used in a nonaqueous electric storage element, to evaluate the adhesion of the positive electrode mixture; no floating or peeling of the positive electrode mixture was observed, and the positive electrode mixture stuck firmly on the aluminum foil. Thus, it was confirmed that the polyphenylene sulfide particles function as a binder.
  • a composite for forming a positive electrode was prepared in virtually the same way as in Application example 4 except that N-methyl-2-pyrrolidone (NMP) was used instead of cyclohexanone.
  • NMP N-methyl-2-pyrrolidone
  • the viscosity of the composite for forming a positive electrode was 13 mPa ⁇ s.
  • the particle-size distribution of the composite for forming a positive electrode was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 was 2.9 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a positive electrode was satisfactory.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, it was possible to continuously discharge the composite for forming a positive electrode, and the discharge stability of the composite for forming a positive electrode was satisfactory. Also, by printing the composite for forming a positive electrode eight times, it was possible to form a coating film corresponding to around 2.5 mg/cm 2 of the positive electrode mixture, and the printing efficiency of the composite for forming a positive electrode was satisfactory.
  • the aluminum foil having the coating film formed was placed in a dryer at 120 °C for five minutes to dry and remove the solvent, and then, pressed by a roll press machine having the roll temperature set at 150 °C to form a positive electrode mixture so as to prepare a positive electrode.
  • the positive electrode was immersed in propylene carbonate as a nonaqueous solvent used in a nonaqueous electric storage element, to evaluate the adhesion of the positive electrode mixture; no floating or peeling of the positive electrode mixture was observed, and the positive electrode mixture stuck firmly on the aluminum foil. Thus, it was confirmed that the polyphenylene sulfide particles function as a binder.
  • a composite for forming a positive electrode was prepared in virtually the same way as in Application example 4 except that Toraypearl TM PBT (manufactured by Toray Industries, Inc.) as an aqueous dispersion of 10 mass% of polybutylene terephthalate (PBT) particles having an average particle diameter of 0.5 ⁇ m, a glass transition temperature at 34 °C, and a melting point at 224 °C was used instead of Toraypearl TM PPS (manufactured by Toray Industries, Inc.).
  • Toraypearl TM PBT manufactured by Toray Industries, Inc.
  • PBT polybutylene terephthalate
  • polybutylene terephthalate exists as particles in the composite for forming a positive electrode, and the mixed solution of water and cyclohexanone functions as a dispersion medium.
  • the viscosity of the composite for forming a positive electrode was 10 mPa ⁇ s.
  • the particle-size distribution of the composite for forming a positive electrode was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 was 2.9 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a positive electrode was satisfactory.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, it was possible to continuously discharge the composite for forming a positive electrode, and the discharge stability of the composite for forming a positive electrode was satisfactory. Also, by printing the composite for forming a positive electrode eight times, it was possible to form a coating film corresponding to around 2.5 mg/cm 2 of the positive electrode mixture, and the printing efficiency of the composite for forming a positive electrode was satisfactory.
  • the aluminum foil having the coating film formed was placed in a dryer at 120 °C for five minutes to dry and remove the solvent, and then, pressed by a roll press machine having the roll temperature set at 90 °C to form a positive electrode mixture so as to prepare a positive electrode.
  • the positive electrode was immersed in propylene carbonate as a nonaqueous solvent used in a nonaqueous electric storage element, to evaluate the adhesion of the positive electrode mixture; no floating or peeling of the positive electrode mixture was observed, and the positive electrode mixture stuck firmly on the aluminum foil. Thus, it was confirmed that the polybutylene terephthalate particles function as a binder.
  • a composite for forming a positive electrode was prepared in virtually the same way as in Application example 4 except that 3-methoxy-N,N-dimethylpropionamide was used instead of cyclohexanone.
  • polyphenylene sulfide exists as particles in the composite for forming a positive electrode, and the mixed solution of water and 3-methoxy-N,N-dimethylpropionamide functions as a dispersion medium.
  • the viscosity of the composite for forming a positive electrode was 12 mPa ⁇ s.
  • the particle-size distribution of the composite for forming a positive electrode was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 was 2.9 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a positive electrode was satisfactory.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, it was possible to continuously discharge the composite for forming a positive electrode, and the discharge stability of the composite for forming a positive electrode was satisfactory. Also, by printing the composite for forming a positive electrode eight times, it was possible to form a coating film corresponding to around 2.5 mg/cm 2 of the positive electrode mixture, and the printing efficiency of the composite for forming a positive electrode was satisfactory.
  • the aluminum foil having the coating film formed was placed in a dryer at 120 °C for five minutes to dry and remove the solvent, and then, pressed by a roll press machine having the roll temperature set at 150 °C to form a positive electrode mixture so as to prepare a positive electrode.
  • a composite for forming a positive electrode was prepared in virtually the same way as in Application example 6 except that NMP was used instead of cyclohexanone.
  • polybutylene terephthalate does not exist as particles in the composite for forming a positive electrode.
  • the viscosity of the composite for forming a positive electrode was 14 mPa ⁇ s.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, immediately after the start of printing, discharge defects were found in some nozzles, and as the printing continued, the number of discharge-defective nozzles continued to increase. For this reason, the discharge stability of the composite for forming a positive electrode was inadequate.
  • a composite for forming a positive electrode was prepared by mixing 10 mass% of the positive electrode active material (1); 0.3 mass% of polyvinylidene fluoride called Solef 5130 (manufactured by Solvay); and 89.7 mass% of NMP
  • polyvinylidene fluoride is soluble in NMP.
  • the viscosity of the composite for forming a positive electrode was 11 mPa ⁇ s.
  • the particle-size distribution of the composite for forming a positive electrode was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 of 4.5 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; the height of the peak decreased, a new peak appeared at 11 ⁇ m, and the D 90 was 25 ⁇ m. For this reason, the storage stability of the composite for forming a positive electrode was inadequate.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, immediately after the start of printing, discharge defects were found in some nozzles, and as the printing continued, the number of discharge-defective nozzles continued to increase. For this reason, the discharge stability of the composite for forming a positive electrode was inadequate.
  • Toraypearl TM PPS manufactured by Toray Industries, Inc.
  • Toraypearl TM PPS manufactured by Toray Industries, Inc.
  • aqueous dispersion of 10 mass% of polyphenylene sulfide particles is added with polyoxyethylene cumyl phenyl ether in order to disperse polyphenylene sulfide particles in water.
  • Toraypearl TM PPS manufactured by Toray Industries, Inc.
  • NMP a minute amount of an alcohol component whose boiling point is higher than or equal to the boiling point of water (100 °C) and lower than or equal to the boiling point of NMP (202 °C), and a predetermined amount of NMP were added to a predetermined amount of Toraypearl TM PPS (manufactured by Toray Industries, Inc.) are added, to perform the replacement by decompression.
  • NMP dispersion of polyphenylene sulfide particles 5 g of Toraypearl TM PPS (manufactured by Toray Industries, Inc.), 0.5 g of 2-ethoxyethanol, and 95 g of NMP were added into an eggplant flask, and then, the flask was installed on a rotary evaporator. Next, water and 2-ethoxyethanol were evaporated under conditions of 70 °C and 20 mmHg, followed by ultrasonic treatment. Next, it was filtered through a filter paper called No. 5B made by Kiriyama glass CO., to retain particles of 4 ⁇ m, to obtain an NMP dispersion of polyphenylene sulfide particles.
  • the NMP dispersion of the polyphenylene sulfide particles had a solid content concentration of approximately 5 mass%. Also, the NMP dispersion of the polyphenylene sulfide particles had an average particle diameter of 0.4 ⁇ m.
  • a composite for forming a positive electrode was prepared by mixing 25 mass% of the positive electrode active material (1); 15 mass% of an NMP dispersion of 5 mass% of polyphenylene sulfide particles; 5 mass% of an NMP dispersion of 20 mass% of carbon black (manufactured by Mikuni-Color Ltd.) as a conductive aid; and 55 mass% of a mixed solution of NMP and propylene glycol (mass ratio of 7:3).
  • the particle-size distribution of the composite for positive electrode formation was measured, and it was found that the distribution had a peak at 0.7 ⁇ m and the D 90 was 1.8 ⁇ m. After 24 hours, the particle-size distribution of the composite for forming a positive electrode was measured again; no change was observed in the particle-size distribution, and the storage stability of the composite for forming a positive electrode was satisfactory.
  • a composite for forming a positive electrode was prepared in virtually the same way as in Application example 8 except that the positive electrode active material (2) was used instead of the positive electrode active material (1).
  • a composite for forming a positive electrode was prepared in virtually the same way as in Application example 8 except that the positive electrode active material (3) was used instead of the positive electrode active material (1).
  • the viscosity of the composite for forming a positive electrode was 10 mPa ⁇ s.
  • the composite for forming a positive electrode was printed on aluminum foil as a positive electrode substrate, by using an ink-jet printer EV2500 (manufactured by Ricoh Co., Ltd.). At this time, it was possible to continuously discharge the composite for forming a positive electrode, and the discharge stability of the composite for forming a positive electrode was satisfactory. Also, by printing the composite for forming a positive electrode eight times, it was possible to form a coating film corresponding to around 2.5 mg/cm 2 of the positive electrode mixture, and the printing efficiency of the composite for forming a positive electrode was satisfactory.
  • the viscosity of the composite for forming a positive electrode was 12 mPa ⁇ s.
  • polyphenylene sulfide exists as particles in the composite for forming a negative electrode, and the mixed solution of NMP and propylene glycol functions as a dispersion medium.
  • the viscosity of the composite for forming a negative electrode was 14 mPa ⁇ s.
  • Punching was applied to a positive electrode (or a negative electrode) to obtain a round-shaped electrode having a diameter of 16 mm, and then, the round-shaped electrode is put into a coin-shaped can having the same shape as CR2032, together with a glass filter paper GA-100 (manufactured by ADVANTEC) as a separator, a nonaqueous electrolytic solution, and lithium having a thickness of 200 ⁇ m as a counter electrode, to prepare a nonaqueous electric storage element.
  • GA-100 manufactured by ADVANTEC
  • the nonaqueous electrolytic solution was a mixed solution of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) (mass ratio of 1:1:1) in which 1.5 mol/L of LiPF 6 was dissolved.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Un composite pour former une électrode contient un matériau actif et des particules macromoléculaires, et peut être déchargé par un procédé à jet d'encre. Le composite pour former une électrode est excellent en termes de stabilité au stockage et de stabilité de décharge même lorsque la teneur en matériau actif est augmentée.
PCT/JP2019/010100 2018-03-14 2019-03-12 Composite pour former une électrode, procédé de fabrication d'électrode, et procédé de fabrication d'élément de stockage électrique non aqueux WO2019176965A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/975,968 US20210005876A1 (en) 2018-03-14 2019-03-12 Composite for forming electrode, method of manufacturing electrode, and method of manufacturing nonaqueous electric storage element
EP19715242.4A EP3766111A1 (fr) 2018-03-14 2019-03-12 Composite pour former une électrode, procédé de fabrication d'électrode, et procédé de fabrication d'élément de stockage électrique non aqueux
CN201980017838.2A CN111819709A (zh) 2018-03-14 2019-03-12 用于形成电极的复合材料、电极制造方法和非水蓄电元件制造方法
KR1020207025784A KR20200117014A (ko) 2018-03-14 2019-03-12 전극 형성용 조성물, 전극의 제조 방법, 및 비수계 축전 소자의 제조 방법

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018047355 2018-03-14
JP2018-047355 2018-03-14
JP2019003695A JP2019164993A (ja) 2018-03-14 2019-01-11 電極形成用組成物、電極の製造方法及び非水系蓄電素子の製造方法
JP2019-003695 2019-01-11

Publications (1)

Publication Number Publication Date
WO2019176965A1 true WO2019176965A1 (fr) 2019-09-19

Family

ID=66001280

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/010100 WO2019176965A1 (fr) 2018-03-14 2019-03-12 Composite pour former une électrode, procédé de fabrication d'électrode, et procédé de fabrication d'élément de stockage électrique non aqueux

Country Status (1)

Country Link
WO (1) WO2019176965A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023079428A1 (fr) 2021-11-03 2023-05-11 Pfizer Inc. Polythérapies utilisant un agoniste de tlr7/8

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006164783A (ja) * 2004-12-08 2006-06-22 Nissan Motor Co Ltd 電極、電池、およびその製造方法
US20090152509A1 (en) * 2007-12-18 2009-06-18 Samsung Electronics Co., Ltd. Inkjet printable electrode composition, electrode including the same, and secondary battery including the electrode
JP2010097946A (ja) 2008-10-20 2010-04-30 Samsung Electronics Co Ltd インクジェットプリント用の電極組成物、それを用いて製造された電極及び二次電池
US20130129914A1 (en) * 2003-07-31 2013-05-23 Mori Nagayama Secondary cell electrode and fabrication method, and secondary cell, complex cell, and vehicle
CN105932227A (zh) * 2016-05-27 2016-09-07 佛山市智巢电子科技有限公司 一种喷墨打印制备锂离子电池纳米电极薄膜的方法
JP2018047355A (ja) 2017-12-28 2018-03-29 株式会社サンセイアールアンドディ 遊技機
JP2019003695A (ja) 2018-10-01 2019-01-10 東芝テック株式会社 商品データ登録装置およびプログラム

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130129914A1 (en) * 2003-07-31 2013-05-23 Mori Nagayama Secondary cell electrode and fabrication method, and secondary cell, complex cell, and vehicle
JP2006164783A (ja) * 2004-12-08 2006-06-22 Nissan Motor Co Ltd 電極、電池、およびその製造方法
US20090152509A1 (en) * 2007-12-18 2009-06-18 Samsung Electronics Co., Ltd. Inkjet printable electrode composition, electrode including the same, and secondary battery including the electrode
JP2009152180A (ja) 2007-12-18 2009-07-09 Samsung Electronics Co Ltd インクジェット印刷用電極組成物、これから得られた電極及び二次電池
JP2010097946A (ja) 2008-10-20 2010-04-30 Samsung Electronics Co Ltd インクジェットプリント用の電極組成物、それを用いて製造された電極及び二次電池
CN105932227A (zh) * 2016-05-27 2016-09-07 佛山市智巢电子科技有限公司 一种喷墨打印制备锂离子电池纳米电极薄膜的方法
JP2018047355A (ja) 2017-12-28 2018-03-29 株式会社サンセイアールアンドディ 遊技機
JP2019003695A (ja) 2018-10-01 2019-01-10 東芝テック株式会社 商品データ登録装置およびプログラム

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DELANNOY P-E ET AL: "Ink-jet printed porous composite LiFePO4electrode from aqueous suspension for microbatteries", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 287, 17 April 2015 (2015-04-17), pages 261 - 268, XP029158120, ISSN: 0378-7753, DOI: 10.1016/J.JPOWSOUR.2015.04.067 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023079428A1 (fr) 2021-11-03 2023-05-11 Pfizer Inc. Polythérapies utilisant un agoniste de tlr7/8

Similar Documents

Publication Publication Date Title
US20210005876A1 (en) Composite for forming electrode, method of manufacturing electrode, and method of manufacturing nonaqueous electric storage element
CN109980177B (zh) 电极极片和包含所述电极极片的电化学装置
US9111684B2 (en) Non-aqueous electrolyte storage element
US20180261827A1 (en) Electrode, electrode element, nonaqueous electrolytic power storage device
WO2013035361A1 (fr) Batterie secondaire à électrolyte non aqueux
JP7432608B2 (ja) 正極片、当該正極片を含む電気化学装置及び電子装置
JP7432607B2 (ja) 正極片、当該正極片を含む電気化学装置及び電子装置
US20150303513A1 (en) Nonaqueous electrolytic storage element
JPWO2014147983A1 (ja) 非水電解質二次電池
US11532811B2 (en) Composite material, electrode, electrode device, power storage device and method of manufacturing composite material
US20190020057A1 (en) Positive electrode for lithium-ion secondary battery and lithium-ion secondary battery
JP2011070802A (ja) 非水電解質二次電池
KR101527532B1 (ko) 리튬 확산성이 향상된 전극 활물질 및 이를 포함하는 리튬 이차전지
JP2016046042A (ja) 非水電解液蓄電素子
JP7302165B2 (ja) リチウムイオン二次電池用正極、リチウムイオン二次電池及び正極合材用塗布液
WO2019176965A1 (fr) Composite pour former une électrode, procédé de fabrication d'électrode, et procédé de fabrication d'élément de stockage électrique non aqueux
JP2018147874A (ja) 電極、電極素子、非水電解液蓄電素子
JP2016081801A (ja) 正極用電極、非水電解液蓄電素子
JP2023094687A (ja) 液体組成物、電極、電気化学素子、多層セパレータ、収容容器、電極の製造方法、及び電極の製造装置
US20220223864A1 (en) Negative electrode active material for lithium ion secondary battery, negative electrode, and lithium ion secondary battery including the same
CN115336064A (zh) 锂二次电池
US20230272239A1 (en) Liquid composition, liquid composition for inkjet discharging, device for manufacturing layer containing inorganic oxide, method of manufacturing layer containing inorganic oxide, and electrochemical device
CN110277546B (zh) 正极，锂离子二次电池，以及正极复合材料用涂布液
JP7275675B2 (ja) 複合材料、電極、電極素子、蓄電デバイス
US20240258583A1 (en) Lithium metal secondary battery, secondary battery module, and separator for lithium metal secondary battery

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19715242

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20207025784

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2019715242

Country of ref document: EP

Effective date: 20201014

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载